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By Donald B. Evans, Robert D. Pehlke

The solubility of nitrogen in liquid Fe-B alloys has been measured up to the solubility limit for the formation of boron nitride. The activity coefficient of nitrogen increases with increasing boron content in the range 0 to 7 wt pct B. From experimen -tal data, values have been calculated for the B-N interaction parameter e3 at temperatures in the range 1550" to 1750°C. A value of 0.038 has been estimated for the boron self-interaction parameter eg at 1550°C. The standard free energy of decomposition of boron nitride into the elements dissolved in liquid iron has been determined to be: ?F° = 45,900 -21.25T in the range from 1550° to 1750°C. The nitride is assumed to be of composition BN. BORON nitride has an unusual combination of properties which make it appear attractive in a wide range of engineering applications. Some of its more important and most recent applications are in the nuclear area, particularly in connection with the liquid-metal cooled reactor concept now receiving considerable emphasis. Boron nitride has a high degree of stability at elevated temperatures. It also has excellent ma-chinability and the ease with which its crystals deform suggests applications as a lubricant. These properties stem from a hexagonal layer-type structure similar to the structure of graphite. One of its primary uses to date has been for seals in liquid-metal pumping systems. It is also used in nuclear reactors as an insulating layer to separate two solid metals which are not themselves compatible under the conditions of temperature and atmosphere in which they are used. Its inertness to liquid metals has also suggested use as a mold-release agent in casting processes. In addition to its excellent machinability and reported inertness to liquid metals such as iron, silicon, aluminum, copper, and zinc, boron nitride has high thermal conductivity and excellent thermal shock resistance. This combination of properties would make it appear ideal as a refractory crucible material for refining of high-purity liquid metals, for example high-quality steels. However, since it is known that concentrations of boron as low as 50 ppm can have a marked effect on the physical properties of certain steels,' in particular on the creep and stress-rupture properties, an investigation was undertaken to define accurately the chemical equilibrium among boron, nitrogen, and liquid iron in the range of steelmaking temperatures. EXPERIMENTAL PROCEDURE Two experimental approaches to this problem were employed: a Sieverts' method and a quenching method. In the first method, the Sieverts' technique was used to measure the equilibrium nitrogen solubility in liquid Fe-B alloys of 0 to 7 pct B as a function of nitrogen gas pressure over the melt. The solubility limit of the boron nitride phase formed was determined by the point of departure of the nitrogen absorption from Sieverts' Law. This technique has been applied to liquid Fe-Ti alloys by Rao and parlee,' to liquid Fe-A1 alloys by Evans and Pehlke,3 and to solid Fe-V alloys by Fountain and Chipman.4 In the second method a melt of liquid iron was held in a crucible of boron nitride under a known partial pressure of nitrogen gas. After thermodynamic equilibrium was attained, the melt was quenched in a stream of helium and then analyzed by wet-chemical methods for boron and nitrogen. The Sieverts' apparatus used in the first method was essentially of the same design as the one described by Pehlke and Elliott.5 The charge materials were vacuum-melted high-purity iron (Ferro-vac E) supplied by the Crucible Steel Co. and -325 mesh boron powder supplied by Cooper Metallurgical Associates of Cleveland, Ohio. The boron contained less than 0.02 wt pct O, according to supplier's analysis. Recrystallized alumina crucibles were used to contain the melt. Examination of solidified melts showed these crucibles to be satisfactory with no evidence of any reaction or physical penetration of the crucible wall by the melt. The melt temperature was measured by a disappearing filament-type optical pyrometer sighted vertically downward on the melt surface through a 1/4-in.-diam sight hole in the crucible lid. The pyrometer was calibrated against the melting point of pure iron in the same apparatus, taking the emissivity of

Jan 1, 1964

By Arthur F. Wendt

IN 1697 King William the Third granted unto his well-beloved subject Adolph Philipse, a certain tract of land, now known as Putnam County, N. Y. At the death of Adolph Philipse the land descended by inheritance to his nephew, Frederick Philipse. In 1751 his surviving three children partitioned the surface into nine parcels and divided them equally amongst themselves, but reserved the mineral rights which they held in common. Thus, at this early period in the history of the colonies, the existence of valuable deposits of iron-ores in Putnam County seems to have been a matter of common knowledge. Yet it is only within the last five years that the county has become a prominent, producer of iron-ore. Desultory mining had been carried on before that period at the Sump, Croft, arid Tilly Foster mines, but only a limited output was achieved, and few of our iron-masters suspected the existence of an abundance of good ores only forty miles from New York harbor. The accompanying map shows the location of those deposits of ore which are now generally known, and have been worked to considerable extent. Without doubt there are many more still awaiting the miner's pick, for no systematic exploration has ever been attempted within the borders of the county. Geologically, the occurrence of the ore is a counterpart of that of the New Jersey and Lake Champlain magnetites. The countryrock, and even the physical geography, are identical. Many small lakes dot the surface of the county. It is from these and their tributary springs and streams that the metropolis derives its farfamed Croton water. Abrupt hills divide the lakes and ponds. Some of the lakes, notably Lake Mahopac, are on the crest of hills, and are fed by subterraneous springs. The prominent mines of the county, in the order of their productiveness, are the Tilly Foster, Mahopac, Croton Magnetic, Sump, Croft, and Island mines. Of these, the first two are at present the only producers, and are quite exceptional in their nature. In fact they are the only ones of their kind in the Appalachian range, if not in the world.

Jan 1, 1885

By T. O. Anderson, E. J. Stahl

Tests to increase knowledge concerning the process of hydraulic fracturing have been performed on three wells in the Allegheny field in western New York. The fracture orientation and its physical appearance at the well-bore was determined by impression packers run at appropriate times throughout the program. Fract~tre azi171uth and its dimensions thus determined were compared to the rock properties and treatment conditions. Logs to provide data concerning rock properties and to improve identification of vertical fractures were run before each step of the fracture treatment. Pressure osc~illu~iot~s were studied after each phase of tile treatments surface pressures during treatment. These measurements show that subsurface pressures exhibit many of the same characteristics as surface pressures during treatment of a well; however, transient pressures are dampened and deelayed in time at the bottom of the well when COmpared with surface pressures. Data obtained from this study provides a means to help locale and determine orientation of vertical fractures made in the open wellbore. Although these rests were performed in only one area, much of the information gained may be applied to fracturing programs in orher areas. INTRODUCTION In this study, various tests were made to provide data to better understand formation fracturing in situ. The reservoir studied is the Richburg oil sand which is a part of a series of predominantly grey sandstones and shales with occasional brown sandstone layers, known as the Caneadea unit of the Canadaway group of Upper Devonian age. Average physical characteristics of 12 cored wells in this area are 13-ft thick gross sand formation, 12-ft thick net sand. 1.7 md permeability, 11 percent porosity, 44 percent oil saturation (before secondary recovery) and 16 percent water saturation (before secondary recovery). This particular area of the Allegheny oil field was originally drilled prior to 1890. The first waterflood secondary recovery attempt was made in 1929. The present sustained waterflood development began in 1951 and is being carried out on a 4.5 to 5-acre spacing. Objectives of these tests were to (I) study fracture azimuth and dimension in relation to rock properties and treating conditions, (2) improve fracture identification techniques, (3) compare surface and subsurface pressure during all phases of treatment and (4) compare the periods of the fluid column oscillations occurring after each phase of treatment. Although the areas of investigation listed appear divergent in purpose, the program was designed primarily to increase knowledge of down-hole conditions leading to rock failure and extension of the fracture thus created. TEST PROCEDURES Wells upon which tests were conducted are designated as Wells 1 through 3. Well 2 was located 440 ft north of Well 1, and Well 3 was located approximately 880 ft west of Well 1. Wells 1 and 2 were completed with cable tools, while the producing interval of Well 3 was rotary cored using fresh water as the drilling fluid to obtain oriented cores. Tests were divided into separate phases on each well as the fracturing program progressed and consisted of measurements performed prior to treatment, during and after the formation breakdown operation. during fracture treatment and after treatment. To verify location and azimuth of the fracture created, and to obtain an impression of wellbore irregularities, a packer was used (Fig. 1). This packer was lowered on tubing into the wellbore opposite the interval under study and inflated in stages to allow the impression material to conform to the wall of the wellbore. A magnetic compass was attached to the tool for orientation reference. Impressions made prior to treatment showed no existing fractures in the wells under study. Impressions made after both formation breakdown and treatment pro-

Thomas H. Beddall, so we are informed by Major J. B. Carlock, has been promoted and is now Adjutant of the 1st Battalion, 1st Gas Regi¬ ment. He was awarded, last summer, the Croix de Guerre. R. A. Bull. See letter in Proceedings of Milwaukee Meeting. Captain Stanley C. Bullock's record since entering the service is given as follows in a letter recently received from Mrs. Bullock: Resigned position of mine manager in Chile in November, 1915, to return to England to obtain commission in Royal Engineers. Joined Officers' Training Corps, Dec. 20, 1915. Commission gazetted, Jan. 27, 1916, 2d Lieut., R. E. Landed in France, Feb. 6, 1916. Posted to 179th Tunnelling Co., R. E. Took part in following battles: Somme, 1916; Ypres;1917; Arras, 1917; Somme, March and July, 1917; Messines, 1917. Gazetted: Acting Captain, July 11, 1916; Temp.-Lieutenant, Oct. 26, 1916; Captain, Sept. 29, 1918. Awarded Military Cross, Jan. 1, 1918, for conspicuous bravery and devotion to duty under a heavy enemy gas bombardment, when, by his example and perseverance in spite of every difficulty and obstacle, mining work was successfully completed which was vital for the success of the operations. The Cross was presented to Capt. Bullock by the King, on Sept. 25, 1918. First Lieut. J. J. Cadot, in a letter sent to Mr. H. `V. Hardinge from France, says he has been at the "Front." He also mentions that the Boche "is a good sprinter."

Jan 12, 1918

By C. B. Foraker

THE Magma mine, of the Magma Copper Co., at Superior, Pinal County, Arizona, is 68 miles east of Phoenix and 21 miles west of Miami, Arizona, on highway U. S. 180. TEMPERATURES AND UNDERGROUND WATERS Surface Temperatures.-The average surface dry-bulb temperature at Superior is 72.4º; wet-bulb, 57.4º; with an indicated relative humidity of 38 per cent. The average yearly rainfall from 1921 to 1936, inclusive, was 18.74 in. The maximum condition of the atmosphere is in June, July and August, and the minimum is in January and February. The surface temperatures, of course, influence the temperatures of the down- cast shafts; however, the variation between winter and summer causes a difference of only 2º to 3º in the stopes and working places that are not close to the intake shafts. Average atmospheric conditions are shown in Fig. 1. Rock Temperatures.-Rock temperatures on the deeper levels of the mine are as follows: [ ] There appears to be no difference in rock temperature for any particular horizon of the various formations or in the vein. Water encountered is always the same temperature as the rock from which it flows, and for this reason it is thought that the water is heated by the rock; not the rock by the water. The country rock apparently has been heated by the various intrusions, perhaps the vein itself, and has not yet had time to cool off. The geothermal gradient (Fig. 2) as indicated by the rock temperatures given above is 1 ½ º per 100 feet. Underground Waters.-The underground water varies from 350 to 565 gal. per min., depending on the rainfall. The limestone and other

Jan 1, 1938

By Alan Morris

In a previous paper1 the results of cutting tests on free-cutting brass rod were reported. Investigation was made of the effects of variation in lead content, microstructure and cold drawing. The author's reply to the discussion of that paper includes a study of the directional cutting properties of drawn and annealed rod. The present paper records the results of tests made on series of samples in which the tin, iron and copper contents have been varied. The apparatus used and method of testing are described in detail in the previous paper. The machine is of the pendulum-operated milling type used and described by Airey and Oxford.2 Angular readings of the height to which the pendulum rises after falling from a fixed position, both when a cut is made and when the pendulum swings freely, give the basis for calculation of the energy consumed in making a cut. Careful weighing of the sample before and after cutting gives a measure of the amount of metal removed. The results are expressed in footpoiinds per cubic inch of metal removed, and have been called "unit cutting energy." In the course of the discussion of the author's earlier paper, W. B. Price reported large-scale tests involving some 50,000 lb. of material. These tests indicated that the addition of as much as 0.6 per cent of iron and 0.25 per cent of tin had apparently no adverse effect on the highspeed cutting characteristics of the rod. The rod also contained a small amount of nickel. The test results reported here tend to confirm his observations. Effect of Variation in Tin Content The castings for this series were made 2 by 1 by 9 in. and were processed as follows: 1. Castings were annealed at 500" C. for 7 hr. 2. Cold-rolled to 0.700 in.

Jan 1, 1933

By Woolsey McA. Johnson

In metallurgical circles it is known widely, but somewhat vaguely, that the ease of reduction of metallic oxides depends largely on the way they hare been prepared. It is likewise known that different forms of carbon have different and greatly varying reducing powers. It is the purpose of this paper to show somewhat more definitely and scientifically these facts. Some years ago the writer published an account of pyrometric determinations of the reduction temperature of zinc oxides variously prepared and of several kinds.' In said paper it was shown that the temperature at which zinc oxide evolves zinc according to the equa-tion ZnO + C = Zn + CO depends upon the nature of the two reacting bodies. The determina-tions had a range of accuracy of from 2° to 6°C., whereas differences were found to amount to an extreme of 90' C. So the differences are real ones and must have a definite cause. The equation of boiling water, (H2O)4 D 4 (H2O) has a fixed temperature for equilibrium of 100° C. at 760 mm. pressure. In general, all equations reacting in the liquid or the gaseous phase have well-defined constant physical conditions which govern the equilibrium point and reaction velocities. In a reaction where we have one or more solid phases, the tempera ture conditions requisite for the unbalancing of the stable system are found to vary. These variations are due to the fact that in a solid there is a very complex molecule and it is not a question solely of the tearing away of two interlocked atoms, but also of the destruction of a complex molecule containing hundreds, or possibly thousands, of smaller molecules. In other words, there are two forces to be overcome: a certain

Jan 1, 1914

By Albert R. Ledoux

Discussion of the Paper of Albert R. Ledoux, read at the Atlantic City Meeting, February, 1904. ARTHUR JARMAN, Sydney, New South Wales, Australia' (communication to the Secretary*): Some remarks upon. Dr. Ledoux's interesting paper from one who has not visited America may, I hope, be of interest to members. It appears to me that there is considerable difference between the training of the American and of the British mining engineer. Not that the subjects are different, but rather in the way in which they are handled, the illustrations being, as far as possible, mining in character. Colloquial instruction is unknown in English curricula, but could be introduced with advantage. Students here assure me that an hour of conversation is of tar more use to them than an hour of the best lecturing. In England a school-year of 6 or 7 months would be considered very short indeed; but Americans do not consider it so, for the reason that the rest of the year is mostly spent in acquiring practical acquaintance with their subjects in works or in the field, and the shorter courses, when coupled with this large amount of outside expe¬rience, produce an essentially practical-minded engineer, who is also more of a business man; whereas the English system, though excellent from a scholastic point of view, produces the theoretical rather than the practical man. British schools are waking up, however, and the practical aspect of the engineer's training is receiving greater consideration. Once launched upon his career, the American engineer is immediately called upon to exercise his self-reliance and ingenuity, if he is to retain the confidence of his employers; but what can we say of English directors? In how many cases is the engineer allowed to guide the destinies of his company? Witness several recent cases of gross waste of money upon unsuitable plants, and the perpetuation of prehistoric methods of

Mar 1, 1905

AGGLOMERATION U.S. 4,067,727 - In the sintering of a charge of iron oxide ore, a fuel and a flux on a travelling grate machine, the dust problem is minimized by providing a plurality of cooling zones and by directing heated dust-laden air from a first cooling zone to the sintering zone wherein the dust is filtered from the air by the material being sintered. Air from a further cooling zone can be exhausted directly to the atmosphere. Dust removal in the cooling zone is improved by using a purging zone in which higher pressure air agitates the dust in the sintered material. This patent is a division of U.S. Patent No. 3,973,762, dated Aug. 10, 1976. F. Cappel, assigned to Dravo Corp. Jan. 10, 1978. 6 pp. (75-5). Filed: 4-1-76 (672,748).

Jan 1, 1979

By E. W. Dewing

The nature of solid solutions of sodium in non-paphitic carbon at temperatures near 1000°C has been investigated by an electrolytic technique. The activity coefficient is found to vary strongly with the heat-treatment temperature of the carbon, and an analysis of the energy terms involved suggests that this is due to variations in the Fermi level. The diffusion coefficient for sodium is in the range implying that the sodium atoms (or ions) are not bound to specific sites on the carbon, in agreement with lack of evidence for specific compounds in the activity -composition curves. In the light of These results phenomena occurring in aluminum reduction cell linings are dis-cussed. It is concluded that sodium migrates by diffusion through the carbon lallice and not the pores, and that A14C9 is formed within the lining hy The excess of NaF invariably found in used linings is formed by this reaction and by air oxidation: There has recently been much interest in the swelling of carbon which occurs when it is made cathodic in an aluminum electrolysis cell, and there is general agreement that the phenomenon is due to the penetration of sodium atoms, derived from the reaction on the carbon lattice. (NaF and AlF3 are constituents of the fused-salt electrolyte.) The low-temperature lamellar compounds of potassium with graphite are well-known, and one compound between sodium and graphite has been reported.4 There is, however, virtually no information on the basic chemistry of the interaction of sodium with nongraphitic carbon at high temperatures, although Dell3 has made some fundamental studies of rates of penetration. At the time the present work was carried out these were not available. Rapoport and samoilenkol had measured rates of physical expansion in a dilatometer, using the fractional increase in length of a carbon specimen after electrolysis in a cryolite bath for 2 hr as an index of susceptibility to cathodic swelling. Work here with a similar apparatus showed that expansion (of a 1.5-in.-diam cylindrical specimen) ceased in less than 20 hr, and that the final expansion was much more reproducible than the value at some intermediate time. This suggested that an equilibrium was being set up, and that a thermodynamic approach was required. The results obtained are not as accurate as had been hoped, but they are the only ones of their type available and have enabled useful conclusions to be drawn. The experimental work was divided into two parts: an investigation of the activity-concentration diagram for sodium in carbon, and a rough determination of the diffusion rate. For the former, most of the experiments were made with petroleum coke even though this is not a form of carbon used in cell linings. It has the advantages, however, that it is a homogeneous material, that it is low in ash, and that its structure is reasonably well understood. Anthracites and coal cokes gave results of the same type as obtained with petroleum coke, but the reprodu-cibility from specimen to specimen was extremely poor. EXPERIMENTAL 1) The Activity-Composition Diagram for Sodium in Carbon. The petroleum coke was ground, pressed at 40,000 psi into plates 19 by 9 by 2 mm without added binder, and heat-treated. The sodium activities were established by an electrolytic technique. The carbon was made anodic in a cryolite bath with an aluminum cathode, and a controlled potential, E, applied so that the sodium activity at the anode was given by ln Na = 1n asa - EF/RT [21 where as, is the sodium activity generated by Reaction [I]. The relative activity is sufficient for many purposes and is simply given by The value of Na not at present known, but when the thermodynamics of the Na-A1 system have been worked out it can be derived from the equilibrium

Jan 1, 1963

By D. L. Martin

THAT small amounts of impurities have a harm-J- ful effect on the malleability of metals and alloys is well-known. One common type of em-brittlement involves the formation of a small quantity of eutectic at the grain boundaries, and is typified by sulfur embrittlement of nickel. Another example of eutectic embrittlement—sulfur embrittlement of cobalt—is described in this report. In the preparation of specimens for a study of Co-Pt alloys, it was observed that the hot swagabil-ity of the alloys appeared to be influenced by the grade of cobalt used as melting stock. The cause of the hot-shortness was not traced to any particular impurity, although sulfur was suspected.' The damaging action of sulfur on the malleability of cobalt has not been generally recognized,'; in spite of the fact that the Co-S phase diagram8 eveals the same basic conditions—low solubility and eutectic formation—responsible for sulfur embrittlement of iron and nickel.7, 8 Apparently sulfur embrittlement has not been a serious problem in the fabrication of cobalt alloys. One related factor is likely the limited commercial experience with high cobalt alloys, since the predominant use of cobalt has been in alloys containing less than 75 pet Co. A series of Co-S alloys was prepared and studied to establish the effect of sulfur on the hot working characteristics of cobalt. Specimens, 5/8 in. diam by 4 in. long, were prepared by vacuum melting in magnesium oxide crucibles and casting in a copper mold. Two grades of low sulfur electrolytic cobalt were used as the basic material for the study, one from Johnson, Matthey and Co. and the other from the International Nickel Co. Each contained about 99.5 pet Co and had a nominal sulfur content under 0.005 pet. The sulfur was added initially as cobalt sulfide powder. Later, some low sulfur alloys were prepared by diluting the high sulfur alloys with cobalt. Trouble was experienced in controlling the sulfur content. Apparently much of the cobalt sulfide powder was lost during melting, as most of the samples contained a lower sulfur content than was added. The alloys were evaluated for hot brittleness by heating to 1000°C in a hydrogen furnace and swaging in air. The results of these tests are summarized in Table I. All the alloys containing less than 0.008 pet S were successfully hot swaged to 1/4 in. diam. The bars containing more than 0.015 pet S could not be swaged because of the formation of intercrystal-line cracks similar to those illustrated in Fig. 1. Examination of the microstructure of the cast bars revealed cobalt sulfide eutectic at the grain boundaries, Fig. 2. The sulfide was not always continuous at grain boundaries in bars that were hot embrittled but, in general, the particles did form a network that could account for the brittleness above the eutectic temperature, 880°C. There is no question about the brittle nature of a specimen exhibiting a continuous sulfide network such as is shown in Fig. 2b, though a sulfide distribution similar to that in Fig. 2a is marginal. This particular bar cracked when hot-swaged. However, other bars with lower sulfur content but with some sulfide phase at grain boundaries were successfully worked. The reduction of area of a hot tensile test specimen was also found to be a sensitive indicator of sulfur embrittlement. The variation of reduction of area with sulfur content is shown in Fig. 3 for specimens fractured at 900°C in an evacuated capsule. The ductility of cobalt is greatly reduced when the sulfur content exceeds 0.005 pet. Similar results were obtained for alloys tested at 800°C, below the eutectic temperature. The upper sulfur embrittlement limit of 0.015 pet, Table I, agrees with the observation of Kalmus8 hat

Jan 1, 1957

In a letter to Prof. L. P. Breckenridge, chairman, urging the continua-tion of the Fuel Conservation Committee of the Engineering Council, Edwin Ludlow calls attention to the millions of tons of culm in the an-thracite region that can be utilized in properly equipped plants and the electricity generated transmitted to. New York, Philadelphia, and other nearby cities. He says: "Experiments have shown the economic value of No. 4 Buckwheat, which passes through a 1/16-in. mesh and over a 1/32-in. mesh. Culm passing through a 1/32-in- mesh is pulverized until it passes through a 300 mesh and is then burned under boilers. Two plants of this kind are now in successful operation in the anthracite region. Another rather interesting experiment was using 30 per cent. of this pulverized coal with 70 per cent. of oil in the generation of steam in the place of pure oil. This utilization of the fine anthracite, which has always been a waste product and thrown away, is not only fuel conservation in its truest sense but in the case of a bituminous strike, when no strike is contemplated in the anthracite field, will furnish fuel to manufacturing plants that otherwise would be obliged to shut down."

Jan 12, 1919

By Hugh H. Waesche

Of all the military services, the Signal Corps is the most concerned with piezoelectric minerals because of its function as a supply service to the strategic and tactical military forces. Consequently this paper is written from the point of view of one associated with that organization. The Signal Corps is responsible for the research, development, and supply of communications, radar, and components to the using services of the Department of the Army and to some extent the Other branches of the National Defense Department. Their work therefore includes the study of the sources* characteristics, and application of quartz and other piezoelectric materials. These materials have become a vital consideration in strategic planning and are essential for efficient tactical operation by all the Armed Forces. The Signal Corps at the beginning of world War 11 Was respon-sible for both Army Ground and Air Force electronic equipment. Since that time this Army service organization has probably done more in the development of frequency control devices using piezoelectric materials than any other group. The U.S. Department of the Interior, Bureau of Mines, Minerals yearbook of 1945, shows that during the four war years, 1942 through 1945, 9,598,-410 Ib of quartz crystal were imported for all uses and of this total, 5,168,000 lb were consumed to produce 78,320,-000 crystal units for electronic application. Other government records confirm these data which conclusively show that approximately 53 pct of the crystalline quartz imported was consumed in the production of electronically applied quartz crystal units. It may be assumed that some effort was made to maintain a stockpile over demands for all purposes. and this would mean that the actual percentage of quartz used electronically was considerably over the 53 pct figure. These data only emphasize that electronic application of crystalline quartz was the greatest requirement, and per- haps the actual value in this application to national defense is many times greater in importance than is apparent on first inspection. Current electronic research and development programs of the Armed Forces are planned around the fundamental use of piezoelectric minerals for frequency control and this at present, at least, means quartz. Definition and Early Development The word piezoelectricity is formed from combination of the Greek word "piezein". meaning "to press," and "electricity." It is that property shown by numerous crystalline substances whereby electrical charges of equal and opposite value are produced on certain surfaces when the crystal is subjected to mechanical stress. It appears to be intimately associated with the better known property, pyro-electricity and in fact, the two may be manifestations of the same phenomeuon. This property was discovered by Pierre and Jacques Curie in quartz, tourmaline, and other minerals in 1880 while studying the symmetry of crystals. The converse effect, that is, mechanical strain in the crystal when placed in an electrical field, was predicted by the French physicist, G. Lippman, in 1881, and verified by the Curies almost immediately. As has been the case with many discoveries of similar character in the basic sciences, not much attention was paid to this property for man)- years except as an entertaining curiosity. Between 1890 and 1892 a series of papers was published by W. voigt in which the theoretical physical properties were put into mathematical form. The first practical application of piezoelectricity occurred during World War I when professor P. Langevin of France used quartz mosaics to produce underwater sound waves. The same mosaics were used to pick up the sound reflections from submerged objects which were in turn, amplified by electronic means and used to determine the distances to such objects. This device was intended for use as a submarine detector but development was not completed in time for war service although it was used later for determining ocean depths. About the same time, A. M. Nicholson, of Bell Telephone Laboratories, developed microphones and phonograph pickups using Rochelle salt crystals. A major step in the application of piezoelectric quartz came in 1921, when professor W. G. Cady, of wesleyan university, showed that a radio oscillator could be controlled by a quartz crystal; from that date, this use of quartz has increased steadily, reaching its peak in world war 11 as is shown by the figures previously given. Essentially all American electronic equipment for communication, navigation, and radar, utilized quartz crystals for the exacting frequency control required. Crystalline Minerals with piezoelectric Properties QUARTZ Hundreds of piezoelectric crystalline materials are known, most of which are water soluble. Of these, quartz appears to be without a peer for electronic frequency control. Unfortunately, the quartz must be of superior quality. It must be free of mechanical flaws, essen-tially optically clear, free of both Brazil and Dauphiné twinning and must be, for average uses, over 100 g in weight. Because of these stringent requirements, raw quartz of the quality desired is of rare occurrence. In addition to quartz, several other naturally occurring crystalline materials are known to have the piezoelectric property and could perhaps be substituted for quartz in some applications. These

Jan 1, 1950

By Robert B. Fulton

The objective of this chapter is to discuss the interrelationship between industrial minerals and chemical manufacturing. It is intended to supplement rather than duplicate the commodity chapters. Particular emphasis is given to the pertinent chemical element and to market factors. Condensing this broad subject into a few pages of this handbook permits treating only the most important elements derived from industrial minerals. Hydrocarbons, which quantitatively dominate as raw materials for the chemical industry, are omitted, as are the metallic elements and the minerals covered in other "use" chapters such as phosphorous, potassium and nitrogen for fertilizers, and titanium dioxide for pigments. The remaining six elements of major importance are: boron, bromine, chlorine, fluorine, sodium, and sulfur. These elements are treated individually under separate headings. Table I (Jones, 1973) affords an overview of the main industrial minerals, the chemical products derived from them, and end uses of the products. Salt brines have particular importance as raw material sources for the chemical industry. Table 2 (Anon., 1967) is a chart of the chemical compounds derived from four types of brines: (1) Owens Lake-type brines, which are sources of boron and sodium compounds; (2) Midland-type brines, from which bromine, iodine, and chlorides of calcium, magnesium, potassium and sodium are derived; (3) Searles Lake-type brines, yielding boron, bromine, lithium, magnesium, potassium, and sodium compounds; and (4) Silver Peak-type brines, produced mainly for lithium. Market Attributes Some of the important market traits common to industrial minerals used by the chemical industry are listed below. 1. They are international commodities, such as fluorspar and sulfur, which largely move to foreign consumers. 2. Grade, and freedom from deleterious elements are important factors affecting their usability in chemical processes. An example is salt (NaCl) used in electrolysis where ultrapure evaporated salt is required to meet rigid specifications. 3. Purified products take on the characteristics of specialty items and command a distinctly higher price than the basic commodity from which they are derived. 4. In practically all cases, chemical users require some sort of cleaning or beneficiation of the naturally-occurring mineral to bring it to specification, and individual specifications may vary from user to user for essentially the same use. 5. In some instances it is necessary to strike a balance between what the vendor can supply and what the buyer requires, with the result that specifications have to be eased to afford the needed materials in marginal cases. 6. Because they tend to be bulk commodities, low cost for handling and transportation are important and such costs may limit the area from which a chemical user can draw his supply. For example, fluorspar from China and Thailand normally goes to Japan, while South African fluorspar can go either to Japan or to the US. 7. Shipments are usually in bulk and frequently in multiple-car, full-trainload or full-shipload lots to reduce transport costs, which in turn may require large terminal investment facilities.

Jan 1, 1983

By L. O. Howard

L. D. RICKETTS, New York, N. Y.-The advance which has been made in Smelting has been in the line of cheaper cost of handling, due to larger units and decrease in losses. At the International smelter, Mr. McGregor designed everything to handle the ore under cover. But we do find an unaccounted for loss of 0.7 per cent. of our copper, which is serious. Mr. Wallace has made a suggestion that I think metallurgists ought to know of and think about. He made it years ago-and that is that one of the chief losses is undoubtedly in the charging and discharging of the calcine cars. His idea is that possibly the dryers and heaters might be put immediately over the reverberatories So that they could discharge in conveyors. They could feed on both sides, and thereby the dust raised by discharging in the cars from the hoppers could be overcome. E. P. MATHEWSON, Anaconda, Mont.-I might Say a few words on the plants we have visited So far. I was particularly struck with the cleanliness of the plants, which is next to Godliness. I noticed also that the skull-cracker arrangement they have for handling their converter slag is very good. And they have paid considerable attention to ventilation, and are taking steps to take care of the health of the men. "Safety first" has been well looked after in all the plants we have visited so far. The steel structures are right up to date, and the buildings are of the most modern type, and everything is conveniently arranged. I think the designers of the plants in the Southwest are to be congratulated on what they have done.

Jan 12, 1916

An Appreciation of Dr. Douglas by Dr. ALBERT R. LEDOUX The Bulletins of the American Institute of Mining Engineers and the program of the International Engineering Congress, held last September at San Francisco, called attention to an important feature in the pro¬ceedings of the Congress; viz., the public presentation to Dr. James Douglas of the John Fritz Medal, for notable achievements in mining, metallurgy, education. and industrial welfare. Dr. Douglas' health, unfortunately, did not permit of his taking the journey to California. While he had been willing that the bestowal of the medal should be a public ceremony, his natural modesty made him shrink somewhat from what he considered something of an ordeal, and he begged those who were to take part in it to use restraint in anything which they might have to say as to his work and attainments. It was, therefore, with some considerable satisfaction on his side that he learned that the medal would be given him without a public, ceremony in New York, or elsewhere. . On Dec. 5, 1915, the writer of this had the pleasure of handing him the medal, certificate, and official letters of transmittal, at his home at Spuyten Duyvil, where lie was surrounded by his children and grandchildren, with one or two of his most intimate friends. He begged the writer to return his thanks to the Committee of Award; and again to express the feeling that nothing in his career merited so great an honor. On this point all of the members of the Institute will share the writer's feeling that Dr. Douglas is too modest. James Douglas was born at Quebec, Canada, in November, 1837. His father Was a distinguished physician and surgeon, employing his skill in the field of philanthropy: He established the first retreat for the insane in the Dominion, to which lie. devoted himself up to the time of his departure from Canada, when it was taken over by the Government. The son spent 2 years in study at the University of Edinburgh, which lie entered in 1855. Returning to Canada, he graduated from Queens University, at Kingston, Ontario, with the degree of Bachelor of Arts, having also studied medicine, and later theology. After his graduation he traveled extensively with his father in Europe and in the Orient, visiting Egypt several time's. They returned with important archaelogical collections, which Dr. Douglas subsequently donated to the Metropolitan Museum of Art in this city. He then returned to Edinburgh, where he continued his course in medicine, surgery being perhaps his chief interest at that time. He was subsequently licensed to preach and his contemporaries bore testimony to his broad philanthropy and to the sympathy which dominated his every act. His taste was distinctly literary; he had carried off a prize at Edinburgh in English literature.

Jan 1, 1916

By Victor Formanek, Paul Chataignon, Maurice Rey

IT is found when floating oxidized lead ores by sulphidization, that the presence of calcium salts in the water, is usually detrimental and lowers the recovery. This effect is particularly marked in dry countries such as North Africa, where the waters often carry large amounts of calcium sulphate and where the ore may even contain gypsum. The effect of calcium salts is readily visible. Whereas in their absence cerussite is quickly stained brown and then black by sodium sulphide, in their presence the mineral remains very light in color. A similar effect is produced when barium sulphide is used as a sulphidizing agent instead of sodium sulphide. Magnesium salts have little or no effect and even tend to reduce the detrimental effect of calcium salts. A study of this phenomenon indicates that it is due to the precipitation of calcium or barium carbonate in contact with the mineral simultaneously with the formation of lead sulphide. The chemical reactions can be interpreted as: PbCO3 + Na2S = PbS + Na2CO3 CaSO4 + Na2CO3 = CaCO3 + Na2 SO4 They might also be written: PbCO3 + S = + Ca++ = PbS + CaCO3 The precipitation of calcium carbonate can be followed by the lowering of the pH with which it is accompanied. Magnesium carbonate is more soluble than calcium carbonate and usually does not precipitate under the conditions prevailing. It is interesting to note that calcium salts have no effect on anglesite (lead sulphate) because calcium sulphate is soluble, but barium salts hinder the sulphidization of anglesite because of the precipitation of barium sulphate. Remedies When calcium sulphate is present in large amounts, the softening of the water with soda ash is usually too expensive to be considered, but the precipitation of the objectionable calcium carbonate can be prevented in two different ways. One is the use of sodium hydrosulphide instead of sodium sulphide. This salt gives a lower pH than sodium sulphide and does not bring about the immediate precipitation of the calcium which remains in solution as calcium bicarbonate. The other procedure is to add ammonium salts such as the sulphate or chloride which have the property of increasing markedly the solubility of calcium carbonate. Ammonium salts have other effects such as cutting down conditioning time and accelerating flotation. They should be added to the flotation cells rather than to the ball mills. Table I. Effect of Sodium Hydrosulphide and/or Ammonium Sulphate on the Flotation of Two Oxidized Lead Ores Mibladen Ore4 La Plagne Ored Con- Tall- Con- Tail-centrate ing centrate ing Reagents Pb, Pct Pb, Pct Pb, Pct Pb, Pot Without addition of CaSO, NaS 56.0 0.68 43.4 0.65 NaSH 56.2 0.60 40.4 0.50 Na2S + (NH4)2SO4d 54.6 0.56 NaSH + (NH4)2SO4d 43.0 0.66 With addition of 40 lb/ton CaSO4 Na2S 39.4 3.85 34.0 3.21 NaSH 49.1 0.70 49.6 0.88 Na2S + (NH4)2SO4d 53.9 0.85 NaSH + (NH4)2SO4d 51.0 0.45 41.1 0.78 In table I are given the results of representative tests on two different oxidized ores. They show that the strongly detrimental effects of calcium sulphate can be offset by the two procedures outlined above. Sodium hydrosulphide is now used regularly on a mill scale on certain ores. Tests are being carried out with ammonium salts. It should be noted that malachite is subject to influences similar to cerussite. One final word of caution—when the ore is rich in primary slime, which is flocculated by the calcium salts, it may be indispensable to remove these by washing or precipitation with sodium carbonate instead of keeping them in solution by the above methods. Acknowledgment We wish to thank Socibtk Miniere & Metallurgique de Penarroya and Minerais et Metaux, for permission to publish these results.

Jan 1, 1951

By Maurice Rey, Victor Formanek, Paul Chataignon

IT is found when floating oxidized lead ores by sulphidization, that the presence of calcium salts in the water, is usually detrimental and lowers the recovery. This effect is particularly marked in dry countries such as North Africa, where the waters often carry large amounts of calcium sulphate and where the ore may even contain gypsum. The effect of calcium salts is readily visible. Whereas in their absence cerussite is quickly stained brown and then black by sodium sulphide, in their presence the mineral remains very light in color. A similar effect is produced when barium sulphide is used as a sulphidizing agent instead of sodium sulphide. Magnesium salts have little or no effect and even tend to reduce the detrimental effect of calcium salts. A study of this phenomenon indicates that it is due to the precipitation of calcium or barium carbonate in contact with the mineral simultaneously with the formation of lead sulphide. The chemical reactions can be interpreted as: PbCO3 + Na2S = PbS + Na2CO3 CaSO4 + Na2CO3 = CaCO3 + Na2 SO4 They might also be written: PbCO3 + S = + Ca++ = PbS + CaCO3 The precipitation of calcium carbonate can be followed by the lowering of the pH with which it is accompanied. Magnesium carbonate is more soluble than calcium carbonate and usually does not precipitate under the conditions prevailing. It is interesting to note that calcium salts have no effect on anglesite (lead sulphate) because calcium sulphate is soluble, but barium salts hinder the sulphidization of anglesite because of the precipitation of barium sulphate. Remedies When calcium sulphate is present in large amounts, the softening of the water with soda ash is usually too expensive to be considered, but the precipitation of the objectionable calcium carbonate can be prevented in two different ways. One is the use of sodium hydrosulphide instead of sodium sulphide. This salt gives a lower pH than sodium sulphide and does not bring about the immediate precipitation of the calcium which remains in solution as calcium bicarbonate. The other procedure is to add ammonium salts such as the sulphate or chloride which have the property of increasing markedly the solubility of calcium carbonate. Ammonium salts have other effects such as cutting down conditioning time and accelerating flotation. They should be added to the flotation cells rather than to the ball mills. Table I. Effect of Sodium Hydrosulphide and/or Ammonium Sulphate on the Flotation of Two Oxidized Lead Ores Mibladen Ore4 La Plagne Ored Con- Tall- Con- Tail-centrate ing centrate ing Reagents Pb, Pct Pb, Pct Pb, Pct Pb, Pot Without addition of CaSO, NaS 56.0 0.68 43.4 0.65 NaSH 56.2 0.60 40.4 0.50 Na2S + (NH4)2SO4d 54.6 0.56 NaSH + (NH4)2SO4d 43.0 0.66 With addition of 40 lb/ton CaSO4 Na2S 39.4 3.85 34.0 3.21 NaSH 49.1 0.70 49.6 0.88 Na2S + (NH4)2SO4d 53.9 0.85 NaSH + (NH4)2SO4d 51.0 0.45 41.1 0.78 In table I are given the results of representative tests on two different oxidized ores. They show that the strongly detrimental effects of calcium sulphate can be offset by the two procedures outlined above. Sodium hydrosulphide is now used regularly on a mill scale on certain ores. Tests are being carried out with ammonium salts. It should be noted that malachite is subject to influences similar to cerussite. One final word of caution—when the ore is rich in primary slime, which is flocculated by the calcium salts, it may be indispensable to remove these by washing or precipitation with sodium carbonate instead of keeping them in solution by the above methods. Acknowledgment We wish to thank Socibtk Miniere & Metallurgique de Penarroya and Minerais et Metaux, for permission to publish these results.

Jan 1, 1951

By L. G. Huntley

Discussion of the paper of L. G. HUNTLEY,. presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 102, June, 1915, pp. 1333 to 1349. E. W. SHAW, Washington, D. C. (communication to the Secretary*). -The comparatively great extent and uniform character of the Dakota sandstone make it of great interest to the student of rock pores and the movements of their fluid contents. However, compared with other sands in areas of carbonaceous rocks facts concerning it do not seem to be of such great direct importance to the producer for it has thus far yielded few important pools of oil or gas. Information concerning the sandstone is extensive but scattered, hence a general treatise regarding it-particularly its pores, the fluids they contain, and the movements of the fluids-has been much needed. I therefore feel that the. chief thing to be ,desired concerning Mr. Huntley's paper is that it were more extended, particularly as to the discussion of the data presented. The general structure map of the Dakota is of especial interest. Slight changes in wording seem to be desirable here and there in the paper. For example, at the beginning of the third paragraph one-wonders if flora instead of fauna were not intended. In Figs. 2, 3, 4, and 5 the vertical scale seems incorrect. Concerning the analyses of oil quoted it is noted that they "are given, as indicating what may be expected in different localities." This seems to need modification for the average analysis of oil from Powder River, which indicates for example that this oil begins to boil at 213°C. The fact is that the samples to which this figure refers were taken from seeps long exposed. to the air :find hence the underground Dakota oil of this district no doubt differs profoundly from that which the analysis indicates. The product of a well here would probably differ more in boiling point and other. respects from the samples analyzed than it would from almost any other petroleum in the world. The use of the word synclinorium does not conform to the original definition, but this may be pardonable because misuse of the term, though a different misuse, has become general. Synclinorium is an orographic term and cannot be correctly applied outside of mountain regions, for it is derived in part from the Greek word for mountain. It has, however, been widely used in a purely structural sense for compound syncline. The broad shallow syncline of the Dakota sandstone falls in neither category. Objection might also be made to the use of

Jan 12, 1915

George W. Maynard, New York, N. Y.:—It is well known that there are many magnetite-mines of which the ore is too low-grade for direct use in the blast-furnace. For carrying out the sintering process, the preliminary step, in the case of magnetites, is the separation of the ore from the gangue by magnetic concentration. The resulting fine-grain product is very objectionable in the blast-furnace, and when used must be a very small percentage of the charge. The sintering process has saved the situation by furnishing a product which is absolutely ideal on account of its cellular structure. (In reply to questions by W. J. Tudor, and Joseph W. Richards, the following additional information was given by Dr. Maynard.) The percentage of iron in the product is determined entirely by the degree of concentration of the raw material and is practically not increased by the sintering operation. The magnetic concentrates at Port Henry and at the Benson and one or two other mines contain from 65 to 67 per cent. of metallic iron. The cost of sintering is from 39 to 41 cents per ton of product, including superintendence, depreciation, and repairs. The itemized figures are about as follows : Mixing (including labor), 24; power, 9; ignition, 5; repairs, 3; total, 41 cents. Prof. J. W. Richards, South Bethlehem, Pa.:—From a metallurgical standpoint I question the accuracy of the statement on p. 374: " C.—An increased reducibility of the iron so treated. (This has been conservatively estimated as 5 per cent. better than the best available ore.)" It seems to me that when a material is' sintered in this way, the constituents present, as lime, silica, and alumina, have a chance to form a compound with the iron oxide; that such a compound, if formed before the material goes into the blast-

Jan 1, 1913